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First-Principles Study of Microscopic Electrochemistry at the LiCoO2 Cathode/LiNbO3 Coating/β-Li3PS4 Solid Electrolyte Interfaces in an All-Solid-State Battery
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First-Principles Study of Microscopic Electrochemistry at the LiCoO2 Cathode/LiNbO3 Coating/β-Li3PS4 Solid Electrolyte Interfaces in an All-Solid-State Battery
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  • Bo Gao*
    Bo Gao
    Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    *Email: [email protected]
    More by Bo Gao
  • Randy Jalem
    Randy Jalem
    Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, Japan
    PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 333-0012, Japan
    More by Randy Jalem
  • Yoshitaka Tateyama*
    Yoshitaka Tateyama
    Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
    Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, Japan
    *Email: [email protected]
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2021, 13, 10, 11765–11773
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https://doi.org/10.1021/acsami.0c19091
Published March 5, 2021

Copyright © 2021 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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High interfacial resistance between electrode and solid electrolyte (SE) is one of the major challenges for the commercial application of all-solid-state batteries (ASSBs), and coating at the interface is an effective way for decreasing the resistance. However, microscopic electrochemistry especially for the electrochemical potential and the distribution of Li+ at the interface has not been well established yet, impeding the in-depth understanding of interfacial Li+ transport. Herein, we have introduced a potential energy profile for Li+, ηLi+, and demonstrated that the interfacial ηLi+ can be evaluated from the calculated interfacial Li vacancy formation energy or the bulk vacancy formation energy and the interface band alignment. Through computational analysis of the representative LiCoO2 cathode/LiNbO3 coating/β-Li3PS4 SE interfaces using the novel interface structure prediction scheme based on the CALYPSO method, we found that ηLi+ at the LiCoO2/β-Li3PS4 interface is highly disordered under the influence of the interface reconstruction and is rather electronic conductive. Insertion of LiNbO3 coating can effectively decrease the preference of ion mixing. Besides, the appropriate changes in band alignments lead to a decrease of difference in the interfacial ηLi+ and lower resistances at the interfaces. The results provide a reliable explanation for the effectiveness of the coating layer observed experimentally. Furthermore, our study provides a guidance for the future simulation of the microscopic electrochemistry at the electrode/SE interfaces in ASSBs.

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Introduction

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As the next-generation energy storage device, all-solid-state batteries (ASSBs) based on inorganic solid electrolytes (SEs) are of great interest due to their improved safety, higher energy density, and superior cycle stability compared to the traditional liquid electrolyte-based Li-ion batteries. (1−4) In the past few years, the Li+ conductivities in the SEs have been significantly improved, which have reached up to 10–2 S cm–1 in some sulfide electrolytes. (5−8) On the other hand, the interfaces between electrodes and SEs also play crucial roles in determining the conductivities of whole batteries. (9−14) It has been reported that the performances of ASSBs are severely limited by high interfacial resistance, (15−20) which has become one of the main problems needed to be solved urgently for practical applications. The insertion of a coating layer has proved to be an effective approach to increase the interfacial Li+ conductivity and suppress the interfacial resistance. (16,17)
The understanding of the underlying mechanism of the interfacial resistance and the coating effect is key for the further optimization of ASSBs. Previous works reported that the high interfacial resistance originates from several factors, such as the formation of the electric double layer or space charge layer, (16,17,21,22) contact loss, (23−25) and interfacial degeneration and reaction. (18,20,26−29) Unraveling the interface Li+ electrochemical potential is key for understanding these interface issues. It is reported that the Li+ electrochemical potential difference between the electrode and the SE is the driving force for the formation of the electric double layer. (16,21,22,30) Besides, our previous calculations have proved that the difference in the potential energy profile of Li+ can act as the migration barrier and leads to the dynamical Li-depletion during charging. (14)
Nowadays, a number of methods have been proposed for describing the electrochemical potentials at the interface between the electrode and solid SE. (17,21,31,32) Some approaches have utilized the bulk properties to calculate the electrochemical potentials. (21) Furthermore, as the interfacial electrochemical potentials rely strongly on the local interface structures, (14) several works have investigated the interface based on the atomistic models and successfully explain some interface phenomena in ASSBs. (14,17,32−34) However, part of the studies employed pristine interface models (17) and mainly focused on the interface Li chemical potential instead of the Li+ electrochemical potential. (14) Moreover, the interfacial band offset, which has a potential influence on the Li+ electrochemical potential, has not been sufficiently discussed yet. (14,17) The interface electrochemistry in ASSBs, as such a fundamental issue, is not well understood yet.
In this work, with direct first-principles calculations of interface models, we investigated the microscopic electrochemistry at LiCoO2 (LCO) cathode/LiNbO3 (LNO) coating/β-Li3PS4 (LPS) SE interfaces, a representative combination in ASSB, to comprehensively understand the mechanisms of interface resistance and coating effect. For the interface structure search, we have employed the interface structure prediction scheme in the CALYPSO methodology. (35−37) The Li vacancy formation energies and the electronic states were examined for the energetically favored interface structures to extract the atomistic mechanism. Throughout these analyses, we also demonstrated that the interfacial electrochemical potential energy profile, ηLi+, can be calculated from the interface vacancy formation energy, or the bulk vacancy formation energy and the interface band alignment. Finally, we showed that coating of LNO can effectively suppress the preference of ion mixing and difference in interfacial ηLi+ to reduce the interfacial resistance. We believe that the present discussion can be a guide for future atomistic simulations of the interface in ASSBs.

Methodology

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The search for energetically favorable structures of the LCO/LNO and LNO/LPS interfaces was performed using an interface structure prediction scheme (14,37) in the CALYPSO methodology. (35,36) Though the amorphous structures are probable in practice, we adopted the crystalline structures and selected the “initial” surface orientations for LCO, LPS, and LNO individually as reasonable models. Note that the final orientation of the interface facet may differ from that of the initial. For LCO, the (104) surface as one of the typical low-energy surfaces has been chosen. (38) For LPS, since the Li+ prefers to migrate along the [010] direction, the (010) surface was selected. (39) For LNO, the (11̅0) surface has been chosen because it has been studied as one of the typical low-index surfaces. (40) Combining our previous investigation of LCO(104)/LPS(010), (14) we can make a unified scenario of the electrochemistry at the LCO cathode/sulfide electrolyte interface. The lattice-matched superlattice of LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) was searched based on the optimized lattice constants of the three crystal structures (see Table S1) using the lattice matching algorithm in CALYPSO methodology and is shown in Table S2. Notably, although the lattice-mismatch strain for the LNO(11̅0)/LPS(010) interface is relatively large (6.86%), we think that this interface can be adopted due to the high ductility of LPS. (39)
The interface structure prediction scheme (14,37) was then used to predict the energetically favorable structures of LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces. Besides the pristine interface, a variety of interfaces with the reaction layers was considered (see Table 1). During the structure prediction, the interface atomic coordinates and the rigid-body displacement between two slabs were regarded as the search dimensions. From 500 to 1500 structures were sampled depending on the structural complexity in each prediction. Moreover, the mutual diffusions of ions were performed in the stable pristine interface models (see Table 1).
Table 1. Calculated γf of the Predicted Energetically Favorable Structures of LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) Interfaces
 γf (eV/nm2)
LCO(104)/LNO(11̅0)
IFpristine0
IFLCO,LNO1.29
IF2LCO,2LNO0.22
IF2LCO,3LNO1.02
IFCo–Nb1.02
LNO(11̅0)/LPS(010)
IFpristine0
IFLNO,LPS–0.06
IF2LNO,2LPS–0.19
IFNb–P–1.31
IFNb(subsurface)–P0.54
IFNb–P(subsurface)–0.41
IFO–S0.78
In our simulations, the slab model was used, which consists of two bulk regions, an interface region, and two vacuum regions. The thin slabs were used in the structure prediction, and they were extended to above 10 Å in the accurate structure optimizations and calculation of properties. To avoid the spurious interaction between the periodic models, the thickness of the vacuum region was set to approximately 15 Å.
The density functional theory (DFT) + U scheme was employed within the generalized gradient approximation of the Perdew, Burke, and Ernzerhof functional (41) as implemented in the Vienna ab initio simulation package. (42) Electron–ion interactions were described using projector-augmented wave pseudopotentials, (43) with the following valence electrons: 2s1 for Li, 2s22p4 for O, 3s23p3 for P, 3s23p4 for S, 3d84s1 for Co, and 4p64d45s1 for Nb. The Hubbard U value (44) was set to 4.91 eV for the Co 3d-state, which is correctly fitted with the redox potential of Co3+ in LCO. (45) In the structure prediction, a plane-wave kinetic energy cutoff of 500 eV and a k-spacing of 0.5 Å–1 in reciprocal space were used to achieve reliable results. For the accurate geometry optimization, the kinetic-energy cutoff and k-spacing were set to 700 eV and 0.25 Å–1 in the reciprocal space, respectively. In the structure optimization, both lattice vector and atomic positions were allowed to be relaxed. Due to the difference in the calculated energies with and without the dipole correction being less than 1 meV/atom, the dipole correction was not involved in the current calculation. To associate with our previous calculations of LCO(104)/LPS(010) interface, (14) the spin-polarized calculation was not involved in the current work and will be carried out in future investigations.
To evaluate the stability of the obtained structures, we defined the interface formation energy with respect to the pristine interface as
(1)
where Etotal and Epristine are the total energies per cell of the simulated and pristine models, respectively. (na, na(pristine)) and (nb, nb(pristine)) are the numbers of f.u. per cell of two materials in the simulated and pristine models, respectively. Ea and Eb represent the energies per f.u. in two bulk phases. A represents the lateral area of the interface per simulated cell.
The energy of Li-vacancy formation with respect to Li metal reservoir at site i was defined as
(2)
where the Etotal(VLi) and Etotal are the total energies of the interfacial structure with and without defect VLi, respectively; and ELi(metal) refers to the energy of Li metal with a body-centered cubic-type structure.
It is noteworthy that −EV(Li) shows the nature of local chemical potential of Li, as proposed in our previous studies. (14,17) We can define the Li energy (chemical potential), ηLi, as −EV(Li). In the calculation of Li vacancy formation energy, the removed Li can be decomposed to the Li+ and e. Therefore, we also introduce ηLi+ and ηe, which are related to the electrochemical potentials of Li+ and electron, respectively. These have a relation that is represented as,
(3)
Especially, ηe is equal to the negative value of the difference in the work functions (Φ) between the calculated interface model and Li metal. The site-dependent ηLi+ can be used to characterize the potential energy surface of Li+ and the Li+ distribution at the interface.
Notably, voltage, which is important in electrochemistry, (32) can be derived from ηLi and Φ. Based on the definition in the study by Leung and Leenheer, (34) the ionic and normal voltages (Vi and Ve) referenced to the Li metal anode can be defined as −(ηLi/e) and −(Φ/e) – 1.37 V, respectively. Here the −1.37 V represents the redox potential of Li+/Li0 below the vacuum level. In this work, we mainly focus on the cathode/SE interface. Note that for calculating the voltage of the whole battery, the effect of the SE/anode interface should be involved as well. The variation of voltage and electrochemical potential of full cell will be studied in future.

Results

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Interface Stabilities and Structures

Through extensive interface structure search based on the CALYPSO methodology, we have successfully predicted a series of energetically low configurations. Here, the interface formation energy (γf) shown in Table 1 is adopted to quantify the stabilities of the predicted LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces. For comparison, we have shown the γf of the selected low-energy structures of the LCO(104)/LPS(010) interface in our previous work (14) in Table S3. Note that the pristine interface was adopted as the referenced model in the calculation of γf. The calculated negative (positive) value of γf means that this interface is energetically more stable (unstable) than the pristine interface.
For the LCO(104)/LNO(11̅0) interface, we have selected five different kinds of interfaces, including the pristine interface (IFpristine), the interface with mutual exchange between Co and Nb (IFCo–Nb), and the interfaces with the reaction layers (IFLCO,LNO, IF2LCO,2LNO, and IF2LCO,3LNO, which are named based on their interfacial atomic compositions). All of the calculated γf values of the reacted interfaces are higher than that of the pristine interface, implying that the pristine interface is energetically the most stable structure, and the ion mixing is unfavorable at this interface. The optimized structures of pristine and metastable interfaces are depicted in Figures 1a and S1, respectively. Especially in the pristine structure, the interface is formed with the interfacial Co–O and Nb–O bonds.

Figure 1

Figure 1. Predicted energetically low interface structures: IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The insets show the enlarged local geometries of the interface structures. The corresponding interface formation energies are listed in Table 1. The green, red, brown, blue, pink, and yellow balls represent the Li, O, Nb, Co, P, and S ions, respectively.

For the LNO(11̅0)/LPS(010) interface, the interfaces with the reaction layers (IFLNO,LPS and IF2LNO,2LPS) have lower γf compared to that of the pristine interface. Especially, the interface with the exchange of the interfacial Nb and P (IFNb–P) with the γf of −1.31 eV/nm2 is the most stable configuration in the predicted structures. However, this γf is still higher than that in the most stable structure (IFCo–P,O–S) of the LCO(104)/LPS(010) interface (−1.40 eV/nm2) (Table S3). We also performed the mutual exchange of the Nb and P in the subsurfaces [IFNb(subsurface)–P and IFNb–P(subsurface)]. The calculated γf values of these configurations are much higher than that of IFNb–P, even though IFNb–P(subsurface) configuration possesses the negative γf value. This indicates that this mutual exchange is mainly localized in the interface region. These results are in good agreement with the previous calculations on the LNO/LPS interface. (33) Besides, in contrast to the LCO(104)/LPS(010) interface, which shows high preference of O–S ion-mixing in our previous study (14)f = −1.30 eV/nm2), the mutual exchange of O and S at this interface is energetically unstable (γf = 0.78 eV/nm2). The optimized interface structures are depicted in Figures 1b,c and S2. Especially, the pristine interface [Figure 1b] is formed with the bonding of the interfacial Nb and S. For the predicted interfaces with the reaction layer and mutual exchanges of ions [Figures 1c and S2], the new Nb–S and P–O polyhedrons are formed at the interface. We expect that the formations of PO4 and PO3S tetrahedrons in these interfaces are energetically favorable, as also observed in the LCO/LPS interfaces, (14) whereas the Nb–S bonds are energetically unfavorable. These competitive bonding behaviors result in the different γf values of the LNO(11̅0)/LPS(010) interfaces.
In summary, the calculated γf reveals that, compared to the LCO(104)/LPS(010) interface, both LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) exhibit lower preferences for the mutual diffusions of ions, which may be helpful for increasing the cycle stability, thereby lowering the interface resistance, as observed in experiments. (15,16,46)

Li Vacancy Formation Energy

We have calculated the interfacial Li vacancy formation energies in the selected LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interface models. The calculated ηLi(interf) is shown in Figure 2. For comparison, the previously calculated ηLi(interf) in LCO(104)/LPS(010) interfaces (14) is depicted in Figure S3. We also calculated the ηLi in the bulk phases [ηLi(bulk)], which are −4.26, −4.99, and −3.32 eV in LCO, LNO, and LPS bulks, respectively.

Figure 2

Figure 2. Calculated ηLi(interf) near the interface region in the low-energy interface models: IFpristine of the LCO(104)/LNO(11̅0) interface (a), and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The color scheme is same as that in Figure 1.

For the LCO(104)/LNO(11̅0) interface, the ηLi(interf) in IFpristine [Figure 2a] is from −3.85 to −4.19 eV in the LCO side and from −3.42 to −3.85 eV in the LNO side. Compared to the values in far from the interface, the fluctuation of ηLi(interf) at the interface is relatively large and some sites with high values (e.g., −3.42 and −3.54 eV) appear because of the structure deformation. Note that the ηLi(interf) in the LCO and LNO sides is higher than the ηLi(bulk) in the bulks. This is due to the rise of the Fermi level in the LCO(104)/LNO(11̅0) interface model, which will be explained in detail in the Discussion section.
For the LNO(11̅0)/LPS(010) interface, the ηLi(interf) in the IFpristine [Figure 2b] and IFNb–P [Figure 2c] has been calculated. Similar to the LCO(104)/LNO(11̅0) interface, the values in IFpristine and IFNb–P are totally shifted up compared to the ηLi(bulk) in LNO and LPS. Especially for IFpristine, ηLi(interf) is from −3.2 to −2.72 eV in the LPS side and from −3.07 to −2.3 eV in the LNO side. The calculated ηLi(interf) in the IFNb–P is similar to that in IFpristine, despite the fact that the values in the LNO side are slightly decreased to −3.32 to −2.93 eV under the effect of the exchange of Nb and P. Note that, under the influence of the interface structure reconstruction, there are some interfacial sites that possess high ηLi(interf) values in IFpristine and IFNb–P.

Electronic Densities of States

In order to understand the electronic properties near the interface, we have calculated the projected densities of states (PDOSs) of the investigated LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces, as depicted in Figure 3. For comparison, the previously calculated PDOSs of LCO(104)/LPS(010) interfaces (14) are depicted in Figure S4 as well.

Figure 3

Figure 3. (Left panels) Calculated layer-decomposed PDOSs for IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The dashed line in each panel indicates the Fermi level. (Right panels) Corresponding layers in the interface models.

For the LCO(104)/LNO(11̅0) interface, the PDOS of IFpristine shows that the valence band in LNO side is located in the deeper region compared with that in the LCO side. The valence band maximum (VBM) is dominated by the Co 3d and O 2p states originating from the topmost layer of LCO. For the IFpristine of the LNO(11̅0)/LPS(010) interface, the valence band in the LPS side is much higher than that in the LNO side, resulting in the S 3p states dominating the VBM. Similar results have also been reported in the previous studies of LCO(110)/LNO(11̅0) and LNO(11̅0)/LPS(010) pristine interfaces. (17) The calculated PDOS of IFNb–P of the LNO(11̅0)/LPS(010) interface shows a similar band alignment with that of IFpristine, although a few electronic states appear in the ion-exchanged region. This indicates that the electronic properties of the LNO(11̅0)/LPS(010) interface is not strongly influenced by the mutual diffusions of ions. These results are distinctly different from those in the LCO(104)/LPS(010) interfaces, where a number of occupied interfacial states induced by the exchange of ions are localized in the band gaps and raises the Fermi levels. (14)

Discussion

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Utilizing the calculated Li chemical potentials and the electronic properties of the low-energy interfaces, we can make a discussion about the Li+ potential energy profile at the LCO cathode/LNO coating/LPS SE interfaces. The schematic illustrations are shown in Figure 4. As the ηLi+ difference between two sides at the interface can determine the distribution of Li+, we focus on the calculation of ηLi+ in the vicinity of the interface. In the cathode and SE bulk phases [Figure 4a], the ηLi+ can be evaluated from eq 3. However, once the electrode is in contact with the SE [Figure 4b], the electrons are redistributed around the interface and the band alignment is changed, leading to a contact potential, which has been found in the previous works. (32,34,47) The ηLi+ and ηe at the interface are varied under the effect of the contact potential. Therefore, it is necessary to calculate ηLi+ in the interface model [ηLi+(interf)]. Note that direct calculation of ηLi+(interf) is difficult because of the charge neutrality constraint. However, since the electrons at the Fermi level [EF(interf)] are to be priorly extracted in the DFT calculation of ηLi(interf), the ηe in eq 3 can be replaced by EF(interf)
(4)

Figure 4

Figure 4. Schematic illustrations of ηLi (green line), ηLi+ (black line) and ηe (red line) in the cathode and SE bulks (a) and in the interface model (b) in ASSBs. Especially in the interface model, the electrons are redistributed at the interface, varying ηLi+ and ηe. The calculations of Li vacancy formation energy with respect to the Li metal in the bulks and interface model are illustrated in (a,b) as well.

Considering the p-type semiconductive property of LCO, the EF(interf) can be estimated from the VBM. The ηLi+ difference between two sides [ΔηLi+(interf)] can be evaluated using
(5)
which demonstrates that the Li vacancy formation energies calculated in our previous works (14,17) can be used to characterize the Li+ potential energy surface at the electrode/SE interfaces in ASSBs.
Here, we also use ηLi(interf) to discuss the Li+ distributions at the interface. Besides being directly calculated from the Li vacancy formation energy in the interface model, ηLi(interf) can also be estimated through the Li vacancy formation energy in the bulks [ηLi(bulk)] and the interface band alignment. Notably, when cathode and SE bulks are in contact with each other, ηLi(bulk) in these two materials is invariant with the change in band alignment at the interface. Therefore, on the basis of eq 4, ηLi(bulk) in both cathode and SE sides can be rewritten as
(6)
Here, ηe(interf) is derived from the VBMs in the bulk region of the interface model. By substituting eq 6 into eq 4, ηLi(interf) in electrode and SE sides can be calculated using
(7)
This equation clarifies the relationship of the calculated ηLi in the bulk and interface models. Note that this formulation neglects the effect of the structure deformation and reconstruction at the interface, which modulates the interfacial ηLi values. Therefore, near the interface, the estimated ηLi(interf) using eq 7 may not well fit with the directly calculated values.
We should point out that the interface atomistic model adopted in this work does not include the Li+ redistribution toward equilibrium because the direct simulation of this process in ASSBs is difficult due to several computational limitations. A large-scale and long-time simulation approach in collaboration with the current method may be a promising way to provide a comprehensive description of the Li+ distribution of a full cell. Nevertheless, the large ΔηLi+(interf) is regarded as a substantial driving force for the interfacial Li+ redistribution. The Li+ in the side with higher ηLi+ values will flow to the other side. As demonstrated in our previous calculations, (14) the |ΔηLi+(interf)| can partially act as the migration barrier of Li+, whose large value will result in the suppression of migration and thus interfacial resistance.
We have summarized the directly calculated ηLi(interf) values in the investigated interface models in Figure 5. The ηLi(interf) evaluated from eq 7 (the values are shown in Table S4) and ηLi(bulk) are also depicted in Figure 5. Moreover, the ionic and normal voltages (Vi and Ve) have been calculated and are shown in Table S4. Due to the interface structure reconstruction, there are some degrees of discrepancy for the ηLi(interf) evaluated from two methods at the interface. Especially near the interface, we have observed some sites with high directly calculated ηLi(interf). This is due to the effect of the interface reconstructions, which create a local region with a distorted structure and relatively unstable sites. Nevertheless, the ηLi(interf) evaluated from eq 7 is in relatively good agreement with the directly calculated values in the regions far from the interface. Based on eq 7, we know that the lower VBM in the bulk region of the interface model compared to the EF(interf) rises the ηLi values. Therefore, since the VBM is much lower than the EF(interf), the calculated ηLi in LNO sides in LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interface models is shifted up by more than 1 eV compared to the values in the LNO bulk.

Figure 5

Figure 5. Calculated ηLi(interf) in the LCO(104)/LPS(010) (a,b), LCO(104)/LNO(11̅0) (c), and LNO(11̅0)/LPS(010) (d,e) interface models. In each figure, the black dots represent the directly calculated values shown in Figure 2. The solid lines refer to the values evaluated from eq 7. For comparison, the ηLi(bulk) is also plotted using dashed lines.

To explain the coating effectiveness of LNO at the LCO/LPS interface observed in experiments, (15,16,46) we have calculated ΔηLi+(interf) derived from ΔηLi(interf). Note that ΔηLi+ equals ηLi+(B) – ηLi+(A) in an A/B interface in our calculations. ΔηLi+ can partially act as the migration barrier of Li+ across the interface. Besides, in order to understand the effect of contact potential (32,34,47) induced from the charge redistribution at the interface, the differences of ηLi+ between bulk phases [ΔηLi+(bulk)] were also calculated. Here, ΔηLi+(bulk) has been calculated from the ηLi(bulk) and ηe(bulk) (see Table S5) through eq 4. From eq 6, we know that
(8)
Here Δηe(bulk) – Δηe(interf) equivalents to the change in the band alignment at the interface, and it also corresponds to the contact potential. The calculated ΔηLi+(interf) and ΔηLi+(bulk) of the investigated interfaces are shown in Table 2. For easier understanding of our results, we have plotted the schematic illustrations of ηLi+ and ηe in the bulk and interface models in Figure S6 on the basis of the calculated results.
Table 2. Calculated ΔηLi+(interf) [ΔηLi(interf)] and ΔηLi+(bulk) for the Investigated LCO(104)/LPS(010), LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) Interfaces
 ΔηLi+(interf) (eV)ΔηLi+(bulk) (eV)
LCO(104)/LPS(010) IFpristine0.601.16
LCO(104)/LPS(010) IFCo–P,O–S–0.351.16
LCO(104)/LNO(11̅0) IFpristine–0.111.45
LNO(11̅0)/LPS(010) IFpristine0–0.29
LNO(11̅0)/LPS(010) IFNb–P0–0.29
Among the three pristine interfaces, the IFpristine of the LCO(104)/LPS(010) interface has the largest ΔηLi+(interf) value (0.6 eV), which acts as the migration barrier, leading to the high interfacial resistance. Although the ΔηLi+(bulk) in IFpristine of LCO(104)/LNO(11̅0) (1.45 eV) is higher than that in the LCO(104)/LPS(010) interface (1.16 eV), the substantial change in band alignment leads to a lower ΔηLi+(interf) (−0.11 eV). The calculated charge difference [Figure S5] indicates that this change in band alignment mainly originates from the electron transfer from the Co ions in the topmost layer of LCO to the bonding O ions in the LNO side. For the IFpristine of the LNO(11̅0)/LPS(010) interface, the absolute value of ΔηLi+(bulk) (−0.29 eV) is less than those in the other two interfaces, and an appropriate contact potential results in a quasi-equilibrium state with the zero ΔηLi+(interf).
The mutual diffusions of ions have been observed at the LCO(104)/LPS(010) and LNO(11̅0)/LPS(010) interfaces. Especially for the LCO(104)/LPS(010) interface (Figure 5b), it is found that the contact potential is noticeably changed, shifting up the ΔηLi+(interf) in the LCO side higher than that in the LPS side in the region far from the interface. Furthermore, as also proposed in our previous study, (14) the ηLi+(interf) in the interface region in IFCo,P–O,S model (equivalent to ηLi(interf) shown as the dot in Figure 5b) is dramatically varied and the sites with remarkably high values appear due to the reconstruction of structure, inducing the high migration barrier across the interface (see Figure S6c), which is unfavorable for the interfacial Li+ transportation. For the LNO(11̅0)/LPS(010) interface, unlike the LCO(104)/LPS(010) interface, the band alignment [Figure 3c] and ΔηLi+(interf) of IFNb–P [Figure 5e] are similar to those in IFpristine, indicating that the electrochemical potentials at this interface is not strongly influenced by the mutual diffusions of ions.
These aforementioned discussions imply that coating of the LNO layer can effectively decrease the preference of mutual diffusions and the Li+ electrochemical difference between LCO and LPS, resulting in a small interfacial resistance, as observed in the experimental works. (15,16,46)
It is noteworthy that, in the LCO/LNO/LPS interfaces, the band alignment plays an important role in decreasing ΔηLi+(interf) between the cathode and SE sides. On the other hand, the band alignment may also contribute to the SE oxidation. As the valence band of LPS is higher than that of LCO in IFCo–P,O–S of the LCO(104)/LPS(010) interface (Figure S4b), the LPS is suggested to be oxidized during charging, which may lead to the degeneration of LPS, thereby further enhancing the interface resistance. In contrast, the lower VBM position of LNO can act as an insulator for preventing the oxidation of the SE induced from the electron transfer from SE to the cathode during charging. Therefore, similar to LNO, the materials with the large band gaps and deep VBMs, such as part of the d0 transition metal oxides (e.g. Li4Ti5O12 (16)), may be suitable as coating materials.

Conclusions

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We have systematically investigated the microscopic electrochemistry at the LCO cathode/LNO coating/LPS electrolyte interfaces in an ASSB using the interface structure prediction scheme implemented in the CALYPSO methodology. We have demonstrated that, in the DFT calculation of interface atomistic model, the Li vacancy formation energies can be used to characterize the Li+ electrochemical potential energy profile. Besides, the Li vacancy formation energy in the interface model can be evaluated from the bulk Li vacancy formation energy and the interface band alignment. Based on the predicted energetically favorable interface configurations, we found that the electrochemical potential energy profile ηLi+ at the LCO(104)/LPS(010) interface is strongly influenced by the mutual diffusions of ions. These quite disordered ηLi+ leads to the high migration barrier and high resistance at the interface. The insertion of the LNO layer between LCO and LPS can effectively decrease the preference of ion mixing. Moreover, the lower VBM position of LNO gives rise to the substantial contact potential at the LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces, resulting in a reasonably uniform ηLi+ and lower interface resistance. Besides, the LNO can also act as an insulator to prevent the oxidation of the sulfide SE during charging. These results successfully explain the effectiveness of the coating of LNO. The other d0 transition metal oxides with large band gap and deeper VBM positions can also be candidates for coating materials. Our study provides general guidelines for the first-principles simulations of the potential energy profiles and distributions of Li+ in the interface atomistic models in ASSBs and probably the other solid-state devices. We believe that the aspects raised here will be also useful for future large-scale simulation for a comprehensive description about the electrochemical potentials of a full cell.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c19091.

  • Lattice parameters calculated in our work and identified in experiments of LCO, LPS, and LNO, selected superlattices for LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces singled out using the lattice matching algorithm in the CALYPSO methodology, interface formation energies of energetically favorable structures of LCO(104)/LPS(010) interfaces, calculated EF(interf) – ηe(interf), ηLi(interf), Vi and Ve in the LCO(104)/LPS(010), LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces, calculated ηLi(bulk) and ηe(bulk) in LCO, LPS and LNO bulks, predicted metastable structures of the LCO(104)/LNO(11̅0) interface, predicted metastable structures of the LNO(11̅0)/LPS(010) interface, calculated ηLi(interf) in the IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated layer-decomposed PDOSs for IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated the charge difference and its average value over the plane parallel to the interface in the IFpristine of LCO(104)/LNO(11̅0) interface, schematic illustrations of the ηLi+ and ηe in the bulk and interface models for LCO(104)/LPS(010), LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces (PDF)

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Author Information

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  • Corresponding Authors
    • Bo Gao - Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanOrcidhttp://orcid.org/0000-0003-1183-656X Email: [email protected]
    • Yoshitaka Tateyama - Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanElements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, JapanOrcidhttp://orcid.org/0000-0002-5532-6134 Email: [email protected]
  • Author
    • Randy Jalem - Center for Green Research on Energy and Environmental Materials (GREEN) and International Center for Materials Nanoarchitectonics (MANA), NIMS, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanElements Strategy Initiative for Catalysts & Batteries, Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245, JapanPRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 333-0012, JapanOrcidhttp://orcid.org/0000-0001-9505-771X
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported in part by JSPS KAKENHI grant number JP19H05815 and by MEXT as “Program for Promoting Researches on the Supercomputer Fugaku” (Fugaku Battery & Fuel Cell Project), grant number JPMXP1020200301, Elements Strategy Initiative, grant number JPMXP0112101003, Materials Processing Science project (“Materealize”), grant number JPMXP0219207397. The calculations were carried out on the supercomputers at NIMS, The University of Tokyo and Kyushu University. This research also used computational resources of supercomputer Fugaku provided by the RIKEN Center for Computational Science (project IDs: hp170054, hp180101, hp200131).

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  • Abstract

    Figure 1

    Figure 1. Predicted energetically low interface structures: IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The insets show the enlarged local geometries of the interface structures. The corresponding interface formation energies are listed in Table 1. The green, red, brown, blue, pink, and yellow balls represent the Li, O, Nb, Co, P, and S ions, respectively.

    Figure 2

    Figure 2. Calculated ηLi(interf) near the interface region in the low-energy interface models: IFpristine of the LCO(104)/LNO(11̅0) interface (a), and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The color scheme is same as that in Figure 1.

    Figure 3

    Figure 3. (Left panels) Calculated layer-decomposed PDOSs for IFpristine of the LCO(104)/LNO(11̅0) interface (a) and IFpristine (b) and IFNb–P (c) of the LNO(11̅0)/LPS(010) interface. The dashed line in each panel indicates the Fermi level. (Right panels) Corresponding layers in the interface models.

    Figure 4

    Figure 4. Schematic illustrations of ηLi (green line), ηLi+ (black line) and ηe (red line) in the cathode and SE bulks (a) and in the interface model (b) in ASSBs. Especially in the interface model, the electrons are redistributed at the interface, varying ηLi+ and ηe. The calculations of Li vacancy formation energy with respect to the Li metal in the bulks and interface model are illustrated in (a,b) as well.

    Figure 5

    Figure 5. Calculated ηLi(interf) in the LCO(104)/LPS(010) (a,b), LCO(104)/LNO(11̅0) (c), and LNO(11̅0)/LPS(010) (d,e) interface models. In each figure, the black dots represent the directly calculated values shown in Figure 2. The solid lines refer to the values evaluated from eq 7. For comparison, the ηLi(bulk) is also plotted using dashed lines.

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  • Supporting Information

    Supporting Information


    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c19091.

    • Lattice parameters calculated in our work and identified in experiments of LCO, LPS, and LNO, selected superlattices for LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces singled out using the lattice matching algorithm in the CALYPSO methodology, interface formation energies of energetically favorable structures of LCO(104)/LPS(010) interfaces, calculated EF(interf) – ηe(interf), ηLi(interf), Vi and Ve in the LCO(104)/LPS(010), LCO(104)/LNO(11̅0), and LNO(11̅0)/LPS(010) interfaces, calculated ηLi(bulk) and ηe(bulk) in LCO, LPS and LNO bulks, predicted metastable structures of the LCO(104)/LNO(11̅0) interface, predicted metastable structures of the LNO(11̅0)/LPS(010) interface, calculated ηLi(interf) in the IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated layer-decomposed PDOSs for IFpristine and IFCo–P,O–S of the LCO(104)/LPS(010) interface, calculated the charge difference and its average value over the plane parallel to the interface in the IFpristine of LCO(104)/LNO(11̅0) interface, schematic illustrations of the ηLi+ and ηe in the bulk and interface models for LCO(104)/LPS(010), LCO(104)/LNO(11̅0) and LNO(11̅0)/LPS(010) interfaces (PDF)


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